Recycled Plastics: Experimental Approaches to Regulatory Compliance

Chapter 10

Recycled Plastics: Experimental Approaches to Regulatory Compliance Robert L. Pesselman and Melanie McCort-Tipton

Downloaded by UNIV OF ARIZONA on January 20, 2013 | http://pubs.acs.org Publication Date: April 20, 2000 | doi: 10.1021/bk-2000-0753.ch010

Covance Laboratories, 3301 Kinsman Boulevard, Madison, WI 53704

The potential for unknown contaminants in the post-consumer plastic recycled stream has raised safety concerns and resulted in regulatory guidelines for food contact polymers. This paper presents an overview of the current regulatory requirements as well as example study designs and experimental results. Model contamination cocktails and analytical methods are outlined. The astounding growth and the advancing technologies in the packaging industry have had a dramatic effect on the regulatory and experimental guidelines for determining the impact of packaging on the safety of food. Regulatory and testing concerns are now focused on adapting to meet the ever-changing needs of the marketplace, as more and newer packaging materials are developed and used. Traditionally, the role of packaging was to prevent contamination. In recent years, new packaging materials and processes have been developed which emphasize convenience for consumers. In addition, making packages tamper-proof has also become a high priority. As a result, packaging has become an integral part of the manufacturing and marketing process. The latest trend in response to consumer demand is to fulfill all of these requirements using biodegradable and recyclable packaging materials. A major change in the industry is the increasing amount of packaging which includes recycled materials. The safety of using these materials in food packaging is a high priority for the packaging industry and for regulators. The primary concern arising from use of recycled materials is the potential for contaminates to end up in packaged foods. Laboratory analysis to detect migration of contaminants into packaged foods is an integral part of ensuring safety and quality in food packaging. In the mid-1980s, researchers at testing facilities began working in close association with packaging

© 1999 American Chemical Society

In Food Packaging; Risch, S.; ACS Symposium Series; American Chemical Society: Washington, DC, 2000.

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104 material manufacturers and food producers in developing methods to ensure the safety of both traditional and recycled materials. Packaging materials Food packaging materials such as glass, paper and tin have been largely replaced by aluminum and plastic. Plastic polymers and laminates are used to make everything from bags and pouches, to trays, bottles, and jars with more new uses being developed every year. Of all packaging materials, plastics is the fastest growing segment of the packaging industry. This is due, in large part to its versatility and ease of use. Packaging accounts for almost 30% of the plastic resins produced per year (approximately 19,551,000,000 lb) . Downloaded by UNIV OF ARIZONA on January 20, 2013 | http://pubs.acs.org Publication Date: April 20, 2000 | doi: 10.1021/bk-2000-0753.ch010

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New packaging materials pose significant challenges to researchers, because some materials have components that can migrate into the packaged food. This is defined as migration of "indirect food additives" and is regulated in the U.S. by the Food and Drug Administration (FDA). Migration of these indirect additives can cause health concerns and adversely affect the taste, color, and aroma of foods. Researchers' primary goal is ensuring that packaging materials will not pose health hazards through migration of indirect food additives. The complexity of this task has been compounded by the increased growth in the use of recycled materials. Recycling Solid waste is a concern for governments worldwide. As more waste gets generated each year, handling methods like landfilling and incineration become more problematic. Plans for reducing solid waste include four methods of management: source reduction (including reuse), recycling, incineration, and landfill. Packaging materials make up over one-third of the total solid waste generated in the United States. While the amount of solid waste increases, so do recycling efforts. The amount of waste recycled has grown from about 10% in 1980 to an estimated 30% by the year 2000. Some packaging materials are recycled much more than others because of their varying makeup and the nature of recycling technology. The recycling of plastics has grown rapidly. In 1994, over 1 billion pounds of postconsumer plastic bottles were recycled. This is an increase of 21 percent over 1993. This expanding use of recycled materials has resulted in increased attention to ensuring the safety of these materials. When evaluating the safety of packaging materials, especially recycled products, there are three key aspects to be considered: the source of the materials, the nature of the process, and the conditions of use. 2

3

Packaging safety regulations New technologies for improving the quality and lessening the environmental impact of packaging have resulted in more recycled, recyclable, and biodegradable packaging. This has resulted in more complex safety issues, revised regulatory guidelines, and a greater need for testing of packaging materials to ensure that unwanted indirect food additives are not migrating into food products. It is important to understand, however, that the safety concerns pertaining to the use of recycled packages are no different than those established for virgin materials. Food packaging safety is regulated by the FDA, based on requirements established by the Food, Drug, and Cosmetic Act of 1938 and the Food Additives Amendment of 1958. Any component of packaging that could migrate into the food is considered an indirect food additive and must be approved by the FDA based on premarket safety testing results submitted by the packaging manufacturer. In Food Packaging; Risch, S.; ACS Symposium Series; American Chemical Society: Washington, DC, 2000.

105 The regulations and guidelines for approval of packaging materials are continually changing due in part to the rapid increase in the number of uses and mixtures of polymers. In general, the following six factors need to be considered for food packaging to be in compliance.


1. 2. 3. 4. 5. 6.

Is the material in contact with the food already regulated by the FDA? Does it contain only additives that are at or below permitted concentrations? To what extent are trace amounts of the constituents of the packaging migrating? What is the total weight of migrating constituents? What is the public health risk of the potential migration? Under what conditions will the packaged product be processed and stored?

In addition, under the provisions of the National Environmental Policy Act of 1968, the FDA is ordered to review the environmental impacts of food packaging materials. In 1995, the FDA adopted a threshold of regulation process for indirect additives. As Bayer noted in his article titled "The threshold of regulation and its application to indirect food additive contaminants in recycled plastics," this threshold "would recognize that there is a level below which the probable exposure to a potentially toxic substance constitutes a negligible risk." He also noted that "This approach, although ultra-conservative, has provided a means for industry and regulators to work together to achieve the goals in reducing municipal solid waste and thereby protect our environment." 5

If the maximum potential dietary concentration of a substance is below 0.5 parts per billion (ppb) and the substance is not a known carcinogen, the FDA considers it to be safe, based on statistical analysis of the available toxicology data. The dietary concentration is calculated by multiplying the fraction of the food in the diet that is in contact with the packaging material (i.e., the consumption factor), times the average concentration of the additive in food. The material can then be used without having to file a formal indirect food additive petition. If the dietary concentration is above 0.5 ppb a different process must be followed. Filing of an indirect additive petition with the FDA is the traditional method to satisfy this requirement. In these instances, the work of testing laboratories has become very important. In addition to safety, studies must clarify the effect packaging may have on taste, odor, and commercial feasibility. Migration testing Migration tests can not only ensure that substances approved as indirect food additives are present at acceptable levels, but identify any components which have not been cleared by the FDA. These tests are required to generate data in support of indirect additive petitions. The major factors to be considered when designing the test methods are the composition of packaged foods, temperatures to which the product and packaging is exposed, the length of time of exposure, and possible migrants such as colorants, plasticizers, and residual monomers. Determining the migration into actual foods has proven difficult because food products, due to their heterogeneous nature, interfere with the tests. As a result, tests are done using food-simulating solvents which simulate the leaching action of aqueous, acidic, alcoholic, and fatty foods. Because the fat content and pH are important factors in migration, the correct simulant must be chosen for each test. 6

The high temperatures to which many multipurpose packages are exposed produce favorable conditions for migration. The time and temperature parameters applicable for analysis are determined by the actual conditions of use.


106 The type of extraction cell required to conduct each test is determined by time and temperature parameters, the type of food contact material, the potential migrants, and the simulants required. Typical extraction cells used are shown in Figure 1. After extraction, the additives are characterized and quantitated using gravimetric, chromatographic, and spectroscopic techniques. The methods used are very sensitive and can detect indirect additives in the low ppb range.


Testing recycled materials The FDA requires that recycled materials must meet the existing purity standards for virgin material. However, safety factors for using recycled materials in packaging are more complex. As a result, even though the regulations are generic, additional characterization and testing beyond that used for virgin materials are required when a recycled product is tested to ensure it is thorough and accurate. In 1992, the F D A published its "Points to Consider for the Use of Recycled Plastics in Food Packaging: Chemistry Considerations." In 1995, a task force formed by the National Food Processors Association and Society of the Plastics Industry, Inc., published their "Guidelines for the Safe Use of Recycled Plastics for Food Packaging Applications." These two sets of guidelines are based upon the collective experience of both the F D A and members of the two associations. The guidelines establish some standards from which to develop a testing strategy. 7

When evaluating the safety of recycled materials, the main concerns are chemical contamination, structural integrity and microbial contamination. These hazards are of more concern with plastics than with glass or metal. This is due to the porous nature of the containers and the fact that plastic containers are often re-used in the home for storing motor oil or for mixing chemicals such as pesticides. Analytical protocols are being developed to demonstrate that contaminant levels in packaging made from recycled materials are sufficiently low to ensure that they can be used safely. The FDA uses three classifications to delineate the approaches to recycling plastic for packaging. These classifications help determine exact methods of testing required. 8

• • •

Primary ( Γ ) recycling is the use of industrial scrap and salvage not yet used by consumers. Secondary (2°) recycling is physical reprocessing of used materials-washing, vacuum and heat treatment, grinding, melting, and reforming. Tertiary (3°) recycling involves chemical reprocessing, purification by a variety of techniques, and repolymerization.

Packaging composed of Γ recycling materials is not considered a hazard to consumers if it is produced according to Good Manufacturing Practices specifications. Manufacturers who produce 2° recycled packaging must have control over the source of the recycled resins and determine restrictions on the types of foods that can be packaged. Packaging made of 3° recycled materials is purified in reprocessing. The high temperatures and solvent baths used in the 2° and 3° processes effectively eliminate exposure to microbiological contaminants. One of the key components of the FDA's report and the Plastics Recycling Task Force was the identification of a set of relatively non-toxic surrogates (i.e., model compounds) for the estimated 60,000 substances that could potentially be found in recycled plastics. The compounds were chosen based on volatility and solubility parameters. This matches the FDA approach of using volatile vs. non volatile and polar vs. non-polar compounds. This was suggested for two primary reasons:


107 1. The solubility of one substance in another substance is a function of the relative polarities of the two 2. The volatility of a substance is a function of its vapor pressure


Some of the suggested surrogates and their corresponding classification are: •

Toluene

Volatile, nonpolar

•

Chloroform

Volatile, polar

•

Lindane

Nonvolatile, nonpolar

•

Diazinon

Nonvolatile, polar

•

Disodium monomethylarsenate

Toxic organo-metal salt

In addition to these surrogates, successful studies that have been acceptable to the FDA have been conducted using other compounds. For example, benzophenone has been used in place of diazinon as a nonvolatile, polar surrogate and phenyldecane and tetracosane have been used as nonvolatile, nonpolar surrogates. In addition, three alternative compounds have been used as toxic salt surrogates: calcium monomethylarsenate (CMMA), copper (H) ethylhexanoate, and zinc stéarate. The use of these alternative surrogates provides several benefits. In most cases the alternates are less toxic thereby increasing safety. In addition, some of the surrogates can be used to simulate more that one type of compound. For example, C M M A may be used as both a nonvolatile-nonpolar surrogate as well as a toxic salt. Study Phases Although the specifics of each study may vary, a typical study for recycled polyethylene terephthalate (PET) may consist of four phases. The phases conducted are dependent upon the levels of simulants found. • •

Phase I: Phase II:

• •

Phase III: Phase IV:

Flake contamination Flake analysis and method validation (before and after processing) Bottle or plaque migration study Extract analysis and method validation

If, after processing, a level of less than 217 ppb is found in flake, migration testing (i.e., Phase III) may not be required. This value may be calculated using the following factors provided by the F D A . 6

•

A consumption factor (CF) of 5% for PET

•

A PET mass/surface area of 0.46g/in .

•

2

2

A 10 g food/in surface area contact

Therefore, 0.5 ppb in the diet calculates to 10 ppb in the food (0.5 ppb/0.05 = 10 ppb) and 10 ppb calculates to a maximum of 217 ppb contamination (10 χ 10" g/g χ 10 g/lin χ lin /0.46g = 217 χ 10' g/g = 217 ppb). 9

2

2

9



One-sided extractions


Nonvolatile analysis


Assembled

determinations

Cell

Ethanol solutions heated boiling point

past

Figure 1. Types of extraction cells.

The bundles pictured in the "Nonvolatile analysis" and "Ethanol solutions heated past boiling point" diagrams are composed of test material sheets and/or plaques that are separated by stainless steel wire mesh to allow the extraction solution to flow freely around the test material.

Support Stand

Volatile


110 Example Studies Study 1 is an example of data generated from the use of contamination cocktails to evaluate a recycle process. In this study, cocktail compounds of chloroform, toluene, lindane, and C M M A were utilized (Table I).


Table I. Recycle Process Study 1 Contamination Cocktail Compounds

% Weight

Chloroform Toluene Lindane CMMA

49.5 49.5 0.5 0.5

Flake Exposure 2 wks @ 40°C

The PET resin was immersed in pure cocktail and stored for two-weeks at 40°C with periodic agitation. The cocktail was then drained-off and the resin air-dried. The contaminated resin was sampled at various stages in the recycling and clean-up process. The resin was subsequently formed into sheets and bottles. Results show that in this example, the recycle process did not reduce the chloroform concentration. The toluene and lindane values in the processed resin were somewhat reduced while the C M M A concentration was significantly lowered to 10 ppm (Table II). Table II. Recycle Process Study 1 Results (ppm) . Contaminated Resin Processed Resin

Chloroform

Toluene

Lindane

CMMA

6,000 7,000

3,000 2,000

200 100

800 10

In Study 2 the surrogate compounds were used individually to intentionally contaminate the PET flake. The contamination conditions for this study can be found in Table III. Table III. Recycle Process Study 2 Contamination Compounds

Flake Exposure

Chloroform Toluene Lindane CMMA

2 secs @ ambient 6 hrs @ ambient 2 secs @ ambient 2 wks @ 40°C

After exposure, each individual PET resin was drained and air-dried. It was then mixed with virgin PET and processed into tubes, preforms, and bottles. Each of these forms was analyzed at various stages of the process to measure the level of contamination during the clean-up process. As the data in Table IV show, the first


Ill step in the process resulted in the greatest reduction in contamination values. Further processing to the preform and bottle stage resulted in no change. Table IV. Recycle Process Study 2 Results (ppm) Chloroform

Toluene

Lindane

CMMA

5,000 2,000 1,000 1,500

2,500 100 50 50

8,000 300 100 150

11,000 300 120 120


Flake Tubes Preforms Bottles

A summary of the analytical methods used to conduct these studies is included in Table V . Migration Studies Generally, laminates which have layers composed of recycled material that do not come in contact with the food product or which contain virgin material as a functional barrier, can be used without concern for contamination. However, regulations require that they must be proven to be safe. These products are tested in extraction studies using intentionally contaminated resins similar to those used in standard Phase III and IV tests. After contamination, analyses are conducted to determine the potential migration through the food-contact layer. Migration studies for PET are conducted using food simulants at 40°C for 30 days. Sampling intervals are 1,3, 10, and 30 days. Typically, only Day 10 and Day 30 intervals are analyzed. Different detection methods are used for PET or ethanol extraction. Validation of these studies is accomplished using the following F D A recommendations: • • •

Standard additions and recovery calculations at 1/2, 1, and 2 times the amount detected. If not detected, validation is conducted at the Limit of Detection Acceptable recoveries 100ppb

60-110% 80-110%

Continuing Challenges The study of packaging design and technology is an ever-changing field. New developments must be vigorously investigated to ensure consumer safety. To that end, tests of food packaging materials must be carefully designed and implemented. Researchers are testing newer degradable materials to determine how much they break down and what components, might migrate into food products. Although some have labeled the FDA approach as conservative, most researchers, regulators, and manufacturers agree that the new guidelines are a major step forward in adopting a process to produce safe recycled plastic products thereby helping to alleviate a major environmental concern. As new methodologies are developed to accomplish this task, we can more accurately document the safety of packaging made from recycled materials. With the knowledge In Food Packaging; Risch, S.; ACS Symposium Series; American Chemical Society: Washington, DC, 2000.

112

Table V. Analytical Method Summaries Lindane


PET lg PET with 10 mL of triflouracetic acid (TFA).

Detection Ethanol 50mL of 10% ethanol is GC using a DB-17 column with extracted with hexane, electron capture detection evaporated, and dissolved in hexane.

TFA solution is extracted with hexane and backwashed with water, evaporated and diluted in hexane. CMMA Detection PET Ethanol lg PET with water in a Parr 25 mL of ethanol extracts are Arsenic determined by hydride generation and atomic absorption bomb and heated to 260°C for 3 pipetted into a vial, hrs. Chloroform

PET lg PET with 5 mL of sulfuric acid in headspace vial

Detection Ethanol Solid phase micro extraction GC using a DB-wax column with (SPME) fiber is used on ethanol electron capture detection extracts. The fiber is thermally desorbed in the GC injection port.

Toluene

PET Ethanol Detection lg PET with 10 mL methylene Solid phase micro extraction GC using a DB-1 column with chloride is shaken for 24 hours (SPME) fiber is used on ethanol flame ionization detection extracts. The fiber is thermally desorbed in the GC injection port. Extract is filtered, passed through a silica gel column into a Kuderna-Danish (KD) flask and concentrated. Benzophenone

Detection Ethanol PET lg PET with trifluoroacetic and Aliquots of ethanol solution are HPLC using a C-18 column with ultraviolet detection shaken. Solutions are extracted injected directly into the HPLC. with hexane, backwashed with water, evaporated, and dissolved in methanol. Copper (II) Ethylhexanoate

PET PET placed in vycor crucible with 4% HC1 and heated to 400°C overnight

Detection Ethanol Aliquots of ethanol solution are Flame atomic absorption for high injected directly into the graphite levels furnace Graphite furnace atomic absorption for low levels


113 gained from these studies, the packaging industry can be more efficient in developing additional recyclable products without increasing the potential for migration of harmful indirect food additives.


Literature Cited 1. The Society of the Plastics Industry. Facts and Figures of the U.S. Plastics Industry. The Society of the Plastics Industry, Inc., Washington, D.C., 1995, pp. 25-26. 2. Environmental Protection Agency. Characterization of Municipal Solid Waste in the United States, 1994 Update. Environmental Protection Agency, Washington, D.C., 1994, pg. 4. 3. Environmental Protection Agency. Characterization of Municipal Solid Waste in the United States, 1994 Update. Environmental Protection Agency, Washington, D.C., 1994, pg. 6. 4. The Society of the Plastics Industry. Facts and Figures of the U.S. Plastics Industry. The Society of the Plastics Industry, Inc., Washington, D.C., 1995, pg. 91. 5. Bayer, Forest L, "The threshold of regulation and its application to indirect food additive contaminants in recycled plastics." Food Additives and Contaminants, 1997, Vol. 14, No. 6-7, pp 661-670. 5. Federal Register, "21 CFR 176.170 Components of paper and paperboard in contact with aqueous and fatty foods." Code of Federal Regulations 21 Parts 170-199, U.S. Government Printing Office, Washington, D.C., 1998, pg. 201. 7. Food and Drug Administration. Points to consider for the use of recycled plastics in food packaging: Chemistry considerations. Center for Food Safety and Applied Nutrition, Washington, D.C.," 1992, pp. 1-3. 8. Food and Drug Administration. Points to consider for the use of recycled plastics in food packaging: Chemistry considerations. Center for Food Safety and Applied Nutrition, Washington, D.C., 1992, pg. 5.


Recycled Plastics: Experimental Approaches to Regulatory Compliance

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